Pyrimidine dyestuffs



United States Patent 01 3,l33,22l Patented May 11, 1955 12 Claims.

This invention relates to Water-soluble organic dyestuffs containing at least one dihalogenated pyrimidine genated pyrimidine ring by another route starting from organic compounds which possess at least one exchangeable hydrogen atom and at least one substituent capable ring, bearing in the 5-position a halogenovinyl or a carboxymethyl group. The process consists in condensing organic dyestuifs which contain at least one, but preferably more than one, water-solubilizing group and at least one exchangeable hydrogen atom, or organic compounds which contain at least one exchangeable hydrogen atom and at least one substituent capable of dyestult formation with a 2.4.G-trihalogenopyrimidine bearing in the 5-position a substituent other than halogen or alkyl, whereupon the reaction products, when they contain radicals of organic compounds with substituents capable of dyestuff formation, are converted into watersoluble dyestuifs by a suitable reaction.

The new process is applicable with all classes of watersoluble dyestuffs. By exchangeable hydrogen atoms are understood, for example, the hydrogen atoms of the hydroxy and thiol groups, but preferably those of the amino group which may be monosubstituted by alkyl, hydroxyalkyl, alkoxyalkyl or halogenoalkyl radicals. Thus, the water-soluble organic dyestuffs of primary interest for the present purpose are those which contain at least one amino group; noteworthy examples of this type are aminomonoazo and aminopolyazo dyestuffs, aminoanthraquinone dyestuffs and aminophthalcyanime dyestuiis. The aminomonoazo and aminopolyazo dyestuifs may contain co-ordinatively bound metal atoms, e.g. chromium, cobalt, nickel or copper atoms. Alternatively, suitable aminoazo dyestufis can be reacted with 2.4.6-trihalogenopyrmidines conforming to the above definition which contain metallizable groupings. The dyestuffs so formed can be metallized in substance after condensation or they can be applied to their fiber in the metal-free form and the dyeings aftertrea-ted with metal-yielding agents.

Further, dyestuffs possessing at least one reactive hydroxy group and those containing a reactive hydroxy group and a reactive, if desired monosubstituted, amino group can -be reacted with 2.4.fi-trihalogenopyrimidines of the type defined. In this reaction the amino and the hydroxy groups can either be combined directly to aromatic nuclei of the dyestuff molecule, or indirectly throughan aliphatic chain and, depending on circumstances, a bridge member.

The following are examples of aliphatic chains:

NHC 0NI-I, NH0 00-- or 1 I- wherein R represents hydrogen, low molecular alkyl or hydroxyalkyl, cycloalkyl, aryl and aralliyl and R" stands for an acyl radical.

In accordance with the definition it is possible to arrive at water-soluble dyestufls containing at least one dihalo- I neutralizing agents.

of dyestutt formation. The azo coupling has a significant bearing on the reaction giving the final dyestufis. It can be eifected by reacting a compound containing at least one exchangeable hydrogen atom and one diazotizable amino group with a 2.4.6-trihalogenopyrirnidine conforming to the above definition, and then diazotizing the intermediate product and coupling the diazo compound with a coupling component to give a water-soluble dyestuit, or by reacting a compound containing at least one exchangeable hydrogen atom and a substituent convertible into a diazotizable amino group with a 2.4.6- trihalogenopyrimidine of the type defined, and converting the said substi-tuent in the intermediate product into the amino group, diazotizing the amino compound, and coupling the diazo compound with a coupling'component to arrive at a water-soluble dyestuif. Alternatively, a 2.4.d-trihalogenopyrimidine conforming to the definition can be reacted with a diarnino compound containing one amino group of high reactivity and a second amino group of low reactivity, whereupon the condensation product, which contains a free amino group and a dihalogenated pyrimidine ring, is employed as diazo component.

Further, it is possible to condense compounds having at least one exchangeable hydrogen atom and at least one carbon atom capable of coupling, e.g. aminohydroxy compounds, with a 2.4.6-trihalogenopyrimidine of the above definition to obtain an intermediate product which is used as coupling component. Naturally, the diazo compound of a diazo component containing a dihalogenopyrimidine ring conforming to the invention can be coupled with a coupling component which likewise contains a dihalogenopyrimidine ring conforming to the invention.

Examples of organic compounds which can be used for producing the pyrimidine dyestuffs are: 1.3- and 1.4- diaminobenzeuesulfonic acids and -carboxylic acids, 4.4- diamino-l.1-diphenyl-3-sulfonic acid, l-(3'- or 4-ami no)-phenyl-3-methyl-5-pyrazolone, amino-hydroxynaphthalenes or preferably, their sulfonic acids, e.g. Z-am-ino- 5-hydroxynaphthalene-7 sulfonic acid, 2-amino-8-hydro- Xynaphthalene-6-sulfonic acid, l-amino-S-hydroxynaphthalene-4.6-disul-fonic acid, l-amino-8-hydroxynaphthalene-3.6-disulfonic acid.

2.4.6-trihalogenopyrimidines conforming to the present definition are the 2.4.6-tribromopyrimidines and, preferably, 2.4.6etrichl-oropyrimidines which may contain in the 5-position a chlorovinyl or a carboxymethyl group.

The reaction of the compounds or water-soluble dyestuffs used as starting products with the 2.4.6-trihalogenopyrimidines of the above definition is carried out preferably in aqueous medium. The halide can be employed as such in concentrated form or in solution in an organic solvent. Solvents specially suitable for halogenopyrimidines are acetone, benzene, chlorobenzene and toluene.

The reaction temperature is varied to suit the reactivity of the individual starting products. If temperatures higher than about 40 C. are necessary it is advisable to Work in vessels equipped with reflux condensers in view of the volatility in steam of the halogenopyrimidines.

The react-ion is conducted in weakly alkaline, neutral to Weakly acid medium preferably in the pH-Iange of 9 to 3. To neutralize the halogen halide formed, an acidbinding agent, e.g. sodium acetate, is added to the solution at the beginning of the reaction, or alternatively small amounts of sodium or potassium carbonate are added in solid powder form or as an aqueous solution during the course of the reaction. Aqueous solutions of sodium or potassium hydroxide are also suitable as The addition of small amounts of areaaaa a wetting or emulsifying agent to the reaction mixture can accelerate the rate of reaction.

In both modes of operation of the process the reaction is conducted in such a manner that only one halogen atom of the 2.4.6-trihalogenopyrimidine reacts with an exchangeable hydrogen atom.

On completion of the condensation or coupling reaction, the solution or suspension may be neutralized if desired, and the final pyrimidine dyestufr' is then salted out with sodium or potassium chloride or precipitated with acid, and filtered with suction, washed and dried.

The water-soluble dyestuffs of the invention which contain at least one dihalogenated pyrimidine ring are suitable for the dyeing, padding and printing of fibers of animal origin, e.g. wool and silk, synthetic polyamide fibers, e.g. nylon, leather, cellulosic fibers, e.g. cotton, linen and hemp, fibers of regenerated cellulose, e.g. viscose filament and staple fibers and cuprammonium rayon, and mixtures of these fibers. The optimum conditions of application vary with the type of fiber and the dyestuffs employed. Animal fibers and synthetic polyarnide fibers are preferably dyed or, in printing, fixed in acid, neutral or weakly alkaline medium, e.g. in presence of acetic acid, formic acid, sulfuric acid, ammonium sulfate, sodium metaphosphate etc. Dyeing can also be carried out in an acetic acid to neutral bath in presence of levelling agents, e.g. polyoxyethylated fatty amines or mixtures of these and alkylpolyglycol ethers; on completion of dyeing the bath is adjusted to the neutral or weakly alkaline region by the addition of small amounts of an agent of alkaline reaction, e.g. ammonia, sodium bicarbonate, sodium hydroxide etc., or compounds which react alkaline on heating, e.g. hexamethylene tetramine or urea. The goods are subsequently rinsed well and, if necessary, soured with a little acetic acid.

In the dyeing and printing of animal and synthetic polyamide fibers the linkage formed between the dyestuff molecule and the fiber is often less pronounced, owing to the fact that some of the dyestuffs by virtue of their acidic character possess afi'inity for the fiber.

The dyeing, padding and printing or fixation of the dyestuff on cellulosic fibers is carried out to best advantage in alkaline medium, e.g. in presence of sodium bicarbonate, sodium carbonate, sodium hydroxide solution, potassium hydroxide solution, sodium metasilicate, sodium borate, trisodium phosphate, ammonia etc. To preclude reduction effects in dyeing, padding or printing it is often of advantage to employ a mild oxidizing agent, e.g. sodium 1-nitrobenzene-3-sulfonate. Fixation of the dyestuffs on cellulosic fibers is generally accomplished with heating. A certain number of the dyestuffs in which the dyestuff molecule is lin red with the dihalogenopyrimidine ring through an oxygen atom can be dyed and/ or fixed at low temperatures, e.g. 20-40 C., by using sufficiently strong alkalis such as sodium or potassium hydroxide or trisodium phosphate.

The dyeings and prints on cellulosic fibers are especially notable for their excellent wet fastness properties .(fastness to water, washing, milling, perspiration and crocking, and their excellent fastness to dry cleaning which are a consequence of the stable chemical linkage formed between the dyestutf molecule and the cellulose molecule. Often the entire amount of dyestuff applied does not take part in the chemical reaction with the fiber. In such cases the portion of unreacted dyestuff is removed from the fiber by suitable treatments, e.g. Washing and/ or soaping, if necessary at high temperatures; for this purpose synthetic detergents can be used, e.g. alkylarylsulfonates, sodium lauryl sulfate, sodium lauryl polyglycol ether sulfate and monoand dialkylphenolpolygylcol others. The dyestuffs reserve cellulose triacetate, polyacrylonitrile and polyethylene terephthalate fibers.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

4 Example 1 57.6 parts of copper phthalocyanine are added to 270 parts of chlorosulfonic acid and the solution heated for 3 hours at 140-145. On cooling to room temperature the reaction mass is poured onto 1500 parts of ice and the suspension formed is filtered off and washed with icecold 1% hydrochloric acid.

The filter cake is mixed with 300 parts of ice and 500 parts of water and the suspension adjusted to pH 7 with sodium hydroxide solution. parts of 1-amino-3-acetylaminobenzene and 100 parts of sodium bicarbonate are added and the mixture stirred for 24 hours. It is subsequently heated for 1 hour at 60, after which 200 parts of 30% hydrochloric acid are added and the suspension formed stirred for 3 hours at 85-90". The intermediate product is filtered off and thoroughly washed with 2% hydrochloric acid.

The filter cake is mixed with 800 parts of water and neutralized with sodium hydroxide solution. 25 parts of 2.4.6.-trichloro-5-(1-chlorovinyl)-pyrimidine are added, followed at 40 by sufiicient sodium hydroxide solution to maintain a constant pH value of 5.5-7.0. As soon as no further sodium hydroxide solution is consumed, the dyestuir is precipitated by the addition of common salt, filtered oil and dried in vacuo at 50. On grinding it is obtained as a dark blue powder which dissolves in water with a turquoise-blue coloration.

A mercerized cotton fabric is padded with a solution at 40 containing 20 g./l. of the dyestuff of this example, 40 g./l. of calcined sodium carbonate and 5 g./l. of sodium 1-nitrobenzene-B-Sulfonate, and squeezed to give an expression or pick-up of 80% to 100%. The padding is fixed by treatment in a conditioning chamber for 4 to 6 hours at 9095 and at constant moisture content. The goods are then well rinsed in cold and hot water, soaped at the boil for minutes with 5 g./l. soap, rinsed again and dried. A brilliant turquoise dyeing of good light and wet fastness is obtained.

Cotton sateen is printed with a paste of the following composition:

30 parts of the dyestufit of the above example, 100 parts of urea, 490 parts of water, 350 parts of a 4% sodium alginate thickening,

30 parts of sodium carbonate 1000 parts total The print is dried, steamed for 10-15 minutes at 102- 104, and rinsed well in cold and Warm water. If necessary it is then soaped at the boil and given a further rinse before drying. A brilliant turquoise-blue print of good light and wet fastness is obtained.

2.4.6-trichloro-5-( l-chlorovinyl)-pyrimidine is obtained by reacting 5 acetylbarbituric acid with phosphorous oxychloride in presence of diethylaniline. The product is purified by distillation in vacuo; it boils at 131-134 at 16 mm. mercury.

By replacing the 2.4.6-trichloro-5-(1-chlorovinyl)-pyrimidine used in this example by the equivalent amount of 2.4.6-tribromo-5-(1' bromovinyl) pyrimidine, a similar dyestufi is obtained.

Example 2 21 parts of 2-(4' amino-2' methyl) phenylazonaphthalene- 4.S-disulfonic acid are dissolved neutral in 250 parts of water with the addition of 30% sodium hydroxide solution. The solution is heated to -85 in a mixing Weset equipped with a reflux condenser, then 13 parts of 2.4.6-trichloro-5-(1' chlorovinyl) pyrimidine are added and the mixture maintained at 75-85 for a few hours with vigorous stirring. The hydrogen chloride formed during the reaction is' continuously neutralized by the addition of dilute sodium carbonate solution so that the pH remains constant at 56. When the reaction has run its course,

which can be easily detected by chromatography, the pyrimidine dyestuif is precipitated by the slow addition of sodium chloride. It is filtered oif and the press cake washed with dilute sodium chloride solution, and dried in vacuo at 80. The resulting dyestuif is a yellow-brown powder which dissolves in water to give yellow solutions.

By replacing the 2.4.6-trichloro 5 (1 chlorovinyl)- pyrimidine by the corresponding amount of 2.4.6-tribromo-5-(l bromovinyl)-pyrimidine, a similar dyestult is obtained.

A fabric, of mercerized cotton is padded with a 3% neutral solution of the dyestuff of this example at a temperature of 50 and an expression (pick-up) of about 85%. It is then dried and the pad-dyeing fixed by treatment for about 45 minutes with good agitation in a developing bath at 70-80 containing 250 parts of anhydrous sodium sulfate and parts of trisodium phosphate per 1000 parts of the solution. The liquor ratio of this bath may be 1:10 to 1:50. After fixation, the material is well rinsed with cold water, soaped twice at the boil, rinsed again and dried. The reddish yellow dyeing obtained possesses excellent fastness to light and wet treatments.

Example 3 23.5 parts of sodium 6-(phenylazo)-2 amino 5 hydroxynaphthalene-7.2'-disulfonate are dissolved in 750 parts of water at pH 4.7 and 50. 1n the course of 45 minutes 25 parts of 2.4.6-trichloro-pyrimidyl- 5 acetic acid are added and the mixture boiled for 5 hours with reflux, the pH value being maintained constant by the addition of sodium carbonate solution. The progress of the reaction can be followed by chromatography on a tale column. On completion of the reaction the dyestufi is precipitated with 200 parts of salt and filtered off. It is purified by redissolution in 560 parts of water and reprecipitation and dried at 60 to give an orange-red powder which has fairly good solubility in water, the solutions being of the same color.

The 2.4.fi-trichloropyrimidyl-S-acetic acid used in this example is produced as follows: Urea is condensed with oc,oc', p-ethanetricarboxylic acid triethyl ester in alcohol containing sodium ethylate, giving barbituryl 5 acetic acid which is suspended in phosphorous oxychloride with the addition of dimethylaniline and heated at 95 for 16 hours. The suspension is then run onto ice, upon which the acid is obtained in solid form; it is filtered ofi and recrystallized from water with the addition of dimethylsulfoxide as small colorless needles of melting point 193-l95.

If the 25 parts of 2.4.-trichloropyrimidyl-S-acetic acid are replaced by 38 parts of 2.4.6-tribromopyrimidyl-5- acetic acid, a similar dyestutf is obtained.

A dyebath is prepared at 50 with 2 parts of the dyestufi dissolved in 5000 parts of water with 3 parts of acetic acid. 100 parts of wool are entered and the temperature increased to the boil in 30 minutes. Dyeing is continued at the boil for 1 hour, then the wool is removed and dried with or without aftertreatment with ammonia. A level dyeing with good light and washing fastness is obtained.

Example 4 10.9 parts of 1-hydroxy-3-amiuobenzene are dissolved in 1000 parts of water with the addition of 8.8 parts of sodium hydroxide. After the addition of 24.5 parts of 2.4.6-trichloropyrimidyl-5-acetic acid the solution is stirred for 3-4 hours at room temperature, whereupon the reaction product which has precipitated as a pulpy crystalline mass is filtered oif.

An amount of the moistpaste equivalent to 31.4 parts of dry x-(3'-arnino)-phenoxy-dichloropyrimidyl-S-acetic acid is mixed with 100 parts of water and 100 parts of 10% hydrochloric acid and diazotized at 0-5" with 25 parts of 4 11 sodium nitrite solution.

For coupling, 28.6 parts of 1acetylamino-8-hydroxynaphthalene-3.d-disulfonic acid are dissolved in 250parts of water and the solution neutralized with sodium hydroxide, cooled to 0-5 and adjusted to pH 4-4.5 with glacial acetic acid. Then the diazo solution is added, the pH re-adjusted to 4-4.5 with sodium acetate and the solution stirred at 5 overnight. The dyestuff is subsequently filtered off and dried at 60. It is a bluish red powder which dissolves with the same coloration in water.

Example 5 50 parts of 1-amino-4-(4'-methylamino)-phenylaminoanthraquinone-2.2disulfonic acid are dissolved in 800 parts of water at 60 with the addition of sodium hydroxide solution at a pH value of 6. Then 26 parts of 2.4.6- trichloro-5-(1'-chlor ovinyl)-pyrimidine are added and the pH maintained between 4.5 and 6 by dropwise addition of dilute sodium hydroxide solution. On completion of condensation the excess of 2.4.6-trichloro-5-(1'-chloro- VinyD-pyrimidine is removed by blowing through steam. 32 parts of potassium chloride are added and the mass allowed to cool with stirring. The precipitated dyestufi is filtered off and dried with vacuum at (SO-.

A dark blue powder is obtained which readily dissolves in water with a blue coloration and dyes fibers of natural and regenerated cellulose in blue shades fast to light, washing, perspiration, water, rubbing and dry cleaning. The dyestufi reserves triacetate, polyester and acrylic fibers.

When the 1-amino-4-(4'-methylamino)-phenylaminoanthraquinone-2.2'-disulfonic acid of this example is replaced by l-amino-4-(4'-amino)-phenylaminoanthraquinone-2.2-disulfonic acid or 1-amino-4-(4'- or 3'-amino)- or 4-(4- or 3'-methylarnino)-phenylaminoanthraquinone-2.6- or -2.7-disulfonic acid, similar dyestuffs are obtained.

Example 6 46.9 parts of the monoazo dyestufi produced by coupling diazotized 3-aminobenzyl alcohol with 1-(2'.5'-dichloro)-phenyl-3-methyl-5-pyrazolone-4'-sulfonic acid in alkaline medium are dissolved neutral in 1600 parts of water at 40. About 50 parts of 30% sodium hydroxide solution are added so that the solution is strongly alkaline to phenolphthalein. It is then cooled to 10 and over the next hour a mixture of 24.2 parts of 2.4.6-trichloropyrimidyl-5-acetic acid in 200 parts of water and 15 parts of 30% sodium hydroxide solution are added. Stirring is continued overnight at 0-3", during which time the new dyestufi precipitates as a gelatinous mass. It is redissolved by adding water and is then salted out with sodium chloride, isolated in the normal manner and dried with vacuum at 60.

The new dyestulf is a yellow powder that dissolves with a greenish yellow coloration in water. On wool, synthetic polyamide fibers and cellulosic fibers it gives bright greenish yellow dyeings and prints of excellent fastness to light and wet treatments.

2 parts of the dyestuff of this example, 0.8 part of an oxethyiated fatty amine and 0.5 part of an oleylpolyglycol ether are dissolved in 5000 parts of water with the addition of 2 parts of glacial acetic acid. The dyebath is heated to 40-50", parts of wool are entered, and it is then brought to the boil in 30 minutes. After boiling for 45 minutes the material is removed, rinsed and dried. A level, greenish yellow shade of very good light and wet fastness is obtained.

Example 7 43.8 parts of the aminoazo dyestulf produced by acid coupling of diazotized 1-amino-4-nitrobenzene with 1- amino-8-hydroxynaphthalene-3.6-disulfonic acid and reduction of the nitro group with sodium sulfide, are dissolved in 400 parts of water with 30% sodium hydroxide solution at 50. The pH of the solution is adjusted to 5. In the course of 45 minutes 48 parts of 2.4.6-trichlorpyrimidyl-S-acetic acid are added and the mixture boiled for 5 hours with reflux with gradual simultaneous addition of sodium carbonate to maintain a constant pH value. The progress of the reaction can be followed by chromatography on a talc column. On completion of the reaction the dyestufr is precipitated with salt, filtered off and washed with a common salt solution. The dyestuif paste obtained is dissolved neutral in 500 parts of water and the solution cooled to To the solution is added the suspension of the diazo compound of 39.2 parts of 1 amino 3 (5 carboxyinethyl dichloro) pyrimidylaminobenzene--sulfonic acid followed by crystallized sodium acetate so that the pH value increases to approximately 6. On the next day the mass is heated to 60 and the disazo dyestuif isolated by salting out and filtration. It is dried to give a black powder.

This dyestufi' is highly suitable for dyeing wool, on which it gives level, full gray to black shades possessing high fastness to light, water, washing, milling, perspiration, crocking and dry cleaning.

The l amino 3 (5 carboxymethyl dichloro)- pyrimidylaminohenzene-6-sulfonic acid used in its production is obtained as follows:

94 parts of 1.3-diaminobenzene-fi-sulfonic acid are dissolved neutral in 1500 parts of water with the addition of a 30% sodium hydroxide solution. The solution is heated to about 50-60 and in 1 hour or so 200 parts of 2.4.6- trichloropyriinidyl-5-acetic acid are added while the pH value is held constant at 55.5 by the addition of sodium carbonate. The mixture is boiled for a few hours with reflux until the reaction is completed, the pH value being maintained constant with sodium carbonate additions. With concentrated hydrochloric acid the solution is then rendered acid to Congo red paper and about one hour later the crystallized reaction product is filtered olf, washed and dried.

Example 8 A similar dyestutf is obtained when l-arnino-4-nitrobenzene-Z-sulfonic acid is used for the acid coupling reaction in place of 1-amino-4-nitrobenzene. Equally valuable are the disazo dyestuffs which are obtained in an exactly analogous manner by coupling 2 moles of diazotized 1-arnino-3 5 carboxymethyl-dichloro -pyrimidylaminobenzene-6-sulfonic acid with 1 mole of l-amino- 8-hydroxynaphthalene-3.6- or -4.6-disulfonic acid.

A dyebath is prepared at 50 with 2 parts of the dyestutf dissolved in 5000 parts of water with 3 parts of acetic acid. 100 parts of wool are entered and the temperature increased to the boil in 30 minutes. Dyeing is continued at the boil for 1 hour, then the wool is removed and dried with or without aftertreatment with ammonia. A level dyeing with good light and washing fastness is obtained.

In the following table are listed the chemical names of dyestuffs free from reactive groups and corresponding to the reactive dyestuffs of the invention which contain a dihalogenopyrimidyl radical bearing in the 5-position a group CCl=CH or -CH -COOH and are obtainable according to the details given in Examples 1 to 8. In these names the hydroxy group or the amino group or groups to which the reactive group is attached, are underlined.

17; 1-ainino-4-[4-(4"-w)-phenyl]-phenylaminoanthraquinone-Z.6.3-trisulfonic acid.

18. Copperphthalocyanine-trisulfonic acid amide-sulfonic acid-(4'-a1nino)-phenylamide.

19. 1-amino-7-(2'-methyl)-phenylazo-S-hydroxynaphthalene-3.6.5-trisulfonic acid.

20. 1-arnin0-7-(2'-methyl)-phenylaz0-S-hydroxy-naphthalene-3.6.4'-trisulfonic acid.

21. 1-a1nino-7-(4'-methoxy)-phenylazo-8-hydroxy-I1aph thalene-3.6.6'-trisulfonic acid.

22. 1-amino-7- (3 '-acetylamino -phenylazo-8-hydroxynaphthalene-3.6.6'-trisulfonic acid.

23. 1-amino-7- (3 '-amino -phenylazo-8-hydroxy-naphthalene-3.6.6'-trisulfonic acid.

24. 1-amino-7-(3-amino-4'-methyl)-phenylazo-8- hydroxy-naphthalene-3.6.6'-trisulfonic acid.

25. 1-amino-7- 3'-trifluoromethyl -phenylazo-8- hydroxynaphthalene-3.6.6'-trisulfonic acid.

26. 1-a1nin0-7-[4'-(6-methy1)-benzothiazolyl-(2")] phenylazo-8hydroxy-naphthalene-3.6.x"-trisulfonic acid.

27. 2-(4'- agino)-phenylazo-naphthalene-4.8-disulfonic acid.

28. 2- (4'-amino-2'-acetylamino -phenylazo-naphthalene-4.8-disulfonic acid.

29. 2- (4'-amino-2"-sulfoacetylamino)-phenylazonaphthalene-4.8-disulf0nic acid.

30. 2- 4'-arnino-3 '-carb oxy) -phenylazo-naphthalene- 4.8-disulfonic acid.

31. 2 (4'-amino-2'-methyl -phenylazo-naphthalene- 5.7-disulfonic acid.

32. 1-phenyl-3-methyl-4-( -a n1i 1 1 )-phenylazo-5- pyrazolone-Z.6-disulfonic acid.

33. 1-[4"-acetylarnino)-stilbenyl-(4')]-3-methyl-4- (S -amino)-phenylazo-S-pyrazolone-Z.2".6'- trisulfonic acid.

34. 1-(2'.5'-dichloro)-phenyl-3-methyl-4-[4'-amin0)- phenyl]-phenylazo-5-pyrazolone-4'.2"-disulfonic acid.

35. 1-[3'-keto-2-(3-an1;ing)-pl1enylazo]-butylraminobenzene-4.6"-disulfonic acid.

3 6. l-naphthyl- (2 -3-methyl-4- (4"-amin0 -pl1enylazo- S-pyrazolone-5'.7'.2"-trisulfonic acid.

37. 1-(2.5'-dichloro)-phenyl-3-methyl-4(4-amino)- phenylazo-5-pyrazolone-4'.2"-disulfonic acid.

38. 1-barbiturylazo-3-amino-benzene-6-sulfonic acid.

39. 1-(2'.5'-dichloro)-phenyl-3-methyl-4-[4-(4"- amino-2'-methyl)-phenyl-3"-methyl]-phenylazo- 5-pyrazolone-4'.6"-disulfonic acid.

40. 1-naphthy1-(2 )-3-methyl-4- (3 "-amino -phenylazo- 5-pyraz0lone-4'.8'.6"-trisulfonic acid.

41. l-phenyl-3-methyl-4-(4"-amino)-phenylazo-5 pyrazolone-Z.5.2"-trisulfonic acid.

42. 1- (3 ai ing -phenylazo-2-hydroxy-naphthalene- 6.6'-disulfonic acid.

43. 1- 3 '-a1nino)-phenylazo-2-hydroxy-naphtl1alene- 8.6'-disulfonic acid.

44. 1-(3'-am1'no)-phenylazo-2-l1ydroxy-naphthalene- 6.8.6'-trisulfonic acid.

45. 1-(3-amino)-phenylazo-2-hydroxy-naphthalene- 3.6.6'-trisulfonic acid.

46. 1- (3 -amino -phenylazo-2-hydroxy-naphthalene- 3.6.8.6-tetrasulfonic acid.

47. l-hydrox -2-(3'-amino)-phenylazo-naphthalene- 3.6-disulfonic acid.

48. l-hydroxy-Z- 3'-amin0 -phenylazo-naphthalene- 4.6'-disulfonic acid.

49. l-hydroxy-Z- (3 '-amino -phenylazo-naphtl1alene- 5.7.6-trisulfonic acid.

50. 1-hydroxy-2(3'-amino)-phenylazo-naphthalene- 3.8.6-trisulfonic acid.

51. 1-hydroxy-2-(3'-amino)-phenylazo-8-chloronaphthalene-3.6.6'-trisulfonic acid.

5 2. l-hydroxy-Z- 3 -amino -phenylazo-S-acetylaminonaphthalene-3.6.6-trisulfonic acid.

2 (2' hydroxy 3 chloro) phenylazo 6 aminonaphthalene-3.5'-disulfonic acid.

113. 1:2 chromium complex compound of 1 hydroxy- 2 (2' hydroxy) naphthyl (1') azo 6 aminonaphthalene-3.4'-disulfonic acid.

114. 1:2 chromium complex compound of 1 hydroxy- 2 (2 hydroxy) phenylazo 6 amino naphthalene 3-sulfonic acid-'-sulfonic acid amide.

115. 1 hydroxy 2 (3' amino) phenylazo naphthalene-4.6.6-trisulfonic acid.

116. 1 hydroxy 2 (3' amino) phenylazo-naphthalene-4.7.6-trisulfonic acid.

117. 1 hydroxy 2 (3' amino) phenylazo naphthalene-3.5.7.6'-tetrasulfonic acid.

118. 1 hydroxy 2 (3 amino) phenylazo naphthalene-3.6.6'-trisulfonic acid-S-sulfonic acid amide. 119. Copper complex compound of 1-l1ydroxy-2-(2-hydroxy) phenylazo 8 amino naphthalene 3.6.5-

trisulfonic acid.

120. Nickel complex compound of 1-hydroxy2-(2'-hydroxy) phenylazo 8 amino naphthalene 3.6.5- trisulfonic acid.

121. Copper complex compound of 1-hydroxy-2-(2'-hydroxy 5' chloro) phenylazo 8 amino naphthalene-3.6.3'-trisulfonic acid.

122. Copper complex compound of 1-hydroxy-2-(2'-hydroxy 3 chloro) phenylazo 8 amino naphthalene-3.6.5'-trisulfonic acid.

123. Copper complex compound of 1 hydroxy-2-(2'-hydroxy 5 methylsulfonyl) phenylazo 8 aminonaphthalene-3.6-disulfonic acid.

124. Copper complex compound of 1-hydroxy-2-(2'-hydroxy) phenylazo 8 -amino naphthalene 3.6 disulfonic acid-5-sulfonic acid amide.

125. Copper complex compound of 1-hydroxy-2-(2'-hydroxy) phenylazo 8 amino naphthalene 3.5.5- trisulfonic acid.

126. Copper complex compound of 1-hydroxy-2-(2'-hydroxy 5 methylsulfonyl) phenylazo 8 aminonaphthalene-3.S-disulfonic acid.

127. Copper complex compound of 1 hydroxy 2 (2'- hydroxy) phenylazo 8 amino naphthalene 3.6.3. 5-tetrasulfonic acid.

128. Copper complex compound of 1-hydroxy-(2-l1ydroxy 3' carboxy) phenylazo 8 amino naphthalene-3.6.5-trisulfonic acid.

129. Copper complex compound of 1-hydroxy-2-(2'-hydroxy) phenylazo 8 -amino naphthalene 3.5.3'.5- tetrasulfonic acid.

130. Copper complex compound of 1-hydroxy-2-(2'-hydroxy 3' carboxy) phenylazo 8 amino naphthalene-3.5.5'-trisulfonic acid.

131. 1 amino 4 (3 amino) phenylamino anthraquinone-Z.6.4'-trisulfonic acid.

132. 1 amino 4 (3' amino) phenylamino anthraquinone-2;4-disulfonic acid.

133. 1 acetylamino 7 (3' hydroxy) phenylazo 8- hydroxy-naphthalene-3.G-disulfonic acid.

134. 1 (4' hydroxy) phenylazo 2 hydroxynaphthalene-3.6-disulfonic acid.

135. 1 (2'.5' dichloro) phenyl 3 methyl 4X3"- amino)-phenylazo-5-pyrozolone 4'.6-disulfonic acid.

136. 1 amino 7 phenylazo 8 hydroxy naphthalene- 3.6.2-trisulf0nic acid.

137. 1 henzoyl 2 hydroxy 6 (4 methylamino)- phenylamino-2-aZabenzanthrone-4.2'-disulfonic acid. 138. 1 acetyl 2 hydroxy 6 (4 amino) phenylamino-3-azabenzanthrone-4.2'-disulfonic acid.

139. 1 carbethoxy 2 methyl 6 (4- amino) phenyl amino-3-azabenzanthrone-4.2'-disulfonic acid.

140. 1 amino 2 (4' isoamyl) phenoxy 4 (4"- amino)-phenylamino-anthraquinone 2.2 disulfonic acid.

12 The dyeings on cotton obtained with the rcactivedyestuffs derived from the dyestuffs No. 9 to 140. have the following shades.

Dyestuff No: Shade 9 Greenish yellow. 10 Do.

11 Red. 12 Yellowish red.

13 Blue. 14 Reddish yellow. 15 Bluish red. 16 Reddish orange. 17 Blue. 18 Turquoise blue. 19 Bluish red.

21 Do. 22 Bluish red.

23 Do. 24 Ruby 25 Red 26 Violet 27 Yellow 28 Reddish yellow. 29 Do.

30 Do. 31 Reddish yellow. 32 Greenish yellow. 33 Yellow. 34 Yellowish orange. 35 Greenish yellow. 36 Reddish yellow. 37 Golden.

38 Greenish yellow. 39 Do.

40 Yellow.

41 Reddish yellow. 42 Orange. 43 Do.

46 Orange red. 47 Orange. 48 Orange red. 49 Yellowish red.

50 Red.

51 Scarlet.

52 Bluish red.

54 Orange. 55 Yellowish red. 56 Do.

57 Scarlet 58 Red 61 Red.

62 Bordeaux.

64 Red.

65 Bluish red.

67 Scarlet 68 Red 72 Red-brown.

73 Brownish orange. 74 Greenish yellow. 75 Dark green.

76 Reddish yellow.

Dyestulf No.: Shade Formulae of representative dyestuffs of the foregoing 77 examples are as follows: 78 Violet-red. 79 Violet-blue. so Violet, 5 Example 1 81 n--. Blue-red. 82 Red-brown. 83 Reddish navy-blue. pp r- Twoaml C1 4 Gray s -NH c1 s Olive-green. J I 5: 86 Reddish navy-blue. IL I 87 Reddish blue. K 88 Do. N 89 Reddish blue. 3? Eli Example 2 92 Reddish blue.

93 Turquoise blue. C1 94 Do. so H G 95 Do. 3 96 I N 0 o=oH 97 Do. NNNH l L 98 Reddish navy-blue. 1 l 99 Navy-blue. CH3 N 100 Brownish violet. 101 Gray. 30311 102 Brownish violet. 103 Greenish gray.

Gray Example 3 105 Reddish navy-blue. 106 Brown. 107 Reddish navy-blue. 108 Brownish violet. SIOBH 01 109 Gray. I 110 Navy-blue. N=N 111 BroWnish violet. N mom-00011 112 Reddish navy-blue. Hots 4 C1 113 Navy-blue. 114 Reddish navy-blue. N 115 Yellowish red. 116 Do. 117 Red-orange. Example 4 11s Red. 119 Violet. 120 Reddish violet. C1 T 121 Bluish violet. 122 Violet. jg G 123 Reddish violet. N o-om-coofl 124 Violet. 01 g fioas- $0111 .125 Reddish violet. y 126 Do. N

127 Violet. 128 D0. 133;::::::::::1:;:::::::::: 521 Example 5 Blue. 132 Reddish blue. 0 133 Bluish red. I I

134 Red. 0 3 135 Greenish yellow. C1 136 Red. 6 CH A 31 137 Violet-re 3 138 Do. ll 1.11011 11 0 01 139 Orange-red. I 140 Blue-violet. a 0 11 N Example 6 01 r a t c I $1 C] C-CH -OOOH 8. The water-soluble organic dyestuif of the formula O-, -NH- and N(CH both halogens of the dihalogenopyrimidyl radicals having the same atomic number from 17 to 35 inclusive.

2. A compound according to claim 1, wherein the azo dyestuff is a water-soluble monoazo dyestutf.

3. A compound according to claim 1, wherein the azo dyestuff is a metal complex compound selected from the group consisting of the 1:2-chromium, 1:2-cobalt, 1:1- nickel and 1:1-copper complex compounds of an azo dyestuff.

4. A compound according to claim 1, wherein the azo dyestulf is a water-soluble disazo dyestuff.

5. A compound according to claim 1, wherein the dyestuif is a water-soluble anthraquinone dyestuff.

6. A compound according to claim 1, wherein the dyestuff is a water-soluble phthalocyanine dyestuff.

7. The water-soluble organic dyestutf of the formula Copper l (S 03H) 3 p11 thalocyanine o S0311 Cl N=NC -NI-I i CC=CH1 Cl $11, 'l ('1- son-r 9. The water-soluble organic dyestutf of the formula 810311 on C1 N o-onrcoon o1 HOaS- NH| 1 J 40 10. The water-soluble organic dyestuif of the formula 01 on Nn-oo-om 01 Ifil o onz-coon HO S- SOJH 11. The water-soluble organic dyestuif of the formula SO3H C1 C1 0H I I N o-o=on 01 3 c-ocn 01 11 O NH- N II I /C N scan N 12. The water-soluble organic dyestutf of the formula I o CN-- -SO=II N/ c-om coon N=NC l ii I o (I:=N

\N% O 2 CH3 References Cited by the Examiner UNITED STATES PATENTS 223,019 12/79 Vaughan 81 2,232,892 2/41 Klenck 81 2,665,273 1/54 Mast et la 260-154 2,935,506 5/60 Heslop et a1 260-154 2,980,665 4/61 Langley 260-454 FOREIGN PATENTS 822,948 11/59 GreatBritain.

CHARLES B. PARKER, Primary Examiner. LEON ZITVER, Examiner. 

1. A DYESTUFF SELECTED FROM THE GROUP CONSISTING OF WATER-SOLUBLE AZO, ANTHRAQUINONE AND PHTHALOCYANINE DYESTUFFS CONTAINING ONE TO TWO DIHALOGENOPYRIMIDYL RADICALS BEARING IN THE 5-POSITION A SUBSTITUENT SELECTED FROM THE GROUP CONSISTING OF CARBOXYMETHYL, A-CHLOROVINYL AND A-BROMOVINYL, THE SAID DIHALOGENOPYRIMIDYL RADICALS BEING CONNECTED TO THE REMAINDER OF THE DYESTUFF MOLECULE BY A BRIDGE SELECTED FROM THE GROUP CONSISTING OF -O-, -NH- AND -N(CH3)-, BOTH HALOGENS OF THE DIHALOGENOPYRIMIDYL RADICALS HAVING THE SAME ATOMIC NUMBER FROM 17 TO 35 INCLUSIVE. 